Detergent compositions containing builders and a urea-olefine-sulfuric acid condensation product



United States Patent 3,384,594 DETERGENT COMPOSITIONS CONTAINING BUILDERS AND A UREA-OLEFINE-SUL- FURIC ACID CONDENSATION PRODUCT Thomas J. Galvin and Francis A. Hughes, Wilmington,

DeL, assignors to Atlas Chemical Industries, Inc., Wilmington, Del., a corporation of Delaware No Drawing. Filed Oct. 21, 1965, Ser. No. 500,256 7 Claims. (Cl. 252137) ABSTRACT OF THE DISCLOSURE Detergent compositions comprising an inorganic detergent builder and a water-soluble salt of an urea-olefin-sulfuric acid condensate. The olefin is either butadiene or a mixture of a major amount of butadiene and a minor amount of cyclopentadiene, unhindered tertiary mono-olefin, 2-alkyl-l,3-butadiene, or mixtures thereof. The condensate may be prepared by adding the olefin to a suspension of urea and sulfuric acid in an inert solvent at a temperature from 10 C. to 70 C.

This invention relates to synthetic detergent compositions, and more particularly concerns synthetic detergent compositions comprising urea-olefin-sulfuric acid condensates.

Synthetic detergent compositions have been known for many years, and, at present, the most widely used and versatile synthetic detergents in commercial use are the branched chain alkyl benzene sulfonates (ABS). It has been estimated that about 75% of all household detergents contain some ABS. These ABS detergents are usually compounded with alkaline builders and frequently contain additives such as brighteners, antiredeposition agents, foaming agents, wetting agents, ion sequestering agents, and the like, to give built or compounded synthetic detergents.

One drawback to the use of ABS is the difiiculty of getting rid of the compound after it has performed its job. Disposal of ABS in sewage, rivers, or ground waters can cause pollution because the ABS is not readily biologically degraded and is not readily precipitated by common chemical coagulants used in sewage treatment. Most organic matter contained in sewage is readily degraded to harmless, low molecular weight compounds by bacteria contained in the sewage but ABS resists the attack of the bacteria. In many sewage treating plants chemical coagulants are employed to fiocculate undesirable matter from the water which is removed by settling or filtering. ABS resists the action of these chemical coagulants (ferric chloride, ferric sulfate, ferrous sulfate, lime, alum, etc.) and continues through the sewage treating plant into the efiluent causing undesirable foaming. Over the past decade, tremendous efforts have been directed toward the discovery of a synthetic detergent which is comparable in detersive characteristics to ABS but which can be readily disposed of after it has performed its job.

It is an object of the present invention to provide detergents which have high detersive characteristics. It is another object of the present invention to provide detergents which are more biodegradable than ABS. It is another object of the present invention to provide detergents which can easily be caused to precipitate from aqueous solutions. It is another object of the present invention to provide detergents which do not cause foam problems. It is another object of the present invention to provide detergents which are economically feasible. It is another ob- 3,384,594 Patented May 21, 1968 ice ject of the present invention to provide detergents which are non-toxic and non-irritating.

Other objects and advantages of this invention will further become apparent in the following description and in the appended claims.

It has now been discovered that the foregoing objects are accomplished by a detergent composition which comprises at least one water-soluble salt of an urea-olefin-sulfuric acid condensation product and at least one builder.

The condensation products of the present invention are condensates of urea, sulfuric acid, and olefin, wherein the olefin is either 1,3-butadiene or a mixture of a major amount of 1,3-butadiene and a minor amount of cyclopentadiene, unhindered tertiary mono-olefin, 2-alkyl-1, 3- butadiene, or mixtures thereof, preferably at least mole percent of the olefin being 1,3-butadiene.

The term unhindered tertiary mono-olefin as used herein denotes tertiary mono-olefins in which carbon atoms alpha, beta, and gamma to the tertiary olefinic carbon atom are free of side chain carbon. The unhindered tertiary mono-olefin can be isobutylene, 2-methyl-1-pentene, 2-methyl-2-butene, Z-methyl-l-butene, Z-methyl-Z pentene, 3-methyl-2-pentene, 2-methyl-l-hexene, Z-methyl- 2-hexene, and the like, The preferred unhindered tertiary mono-olefin being isobutylene. The 2-alkyl-l,3-butadiene is one wherein the alkyl group is unbranched and contains from 1 to 3 carbon atoms, such as Z-methyl-l, 3-butadiene (isoprene), 2-ethyl-l, 3-butadiene, and Z-propyl-l, 3-3- butadiene. The preferred 2-alkyl-1, 3-butadiene is isoprene.

Although the amounts of urea, olefin, and sulfuric acid used to prepare the condensation products can vary widely, the preferred condensates are those which contain on an average, per urea residue, from about 2 to about 50 diolefin residues, from about 0.1 to about 1.5 sulfate groups, and from about 0.1 to about 10 carbon to carbon double bonds.

These condensation products are used in the present invention in the form of their water-soluble salts. Of these, the alkali metal (e.g. sodium and potassium) and ammonium salts are preferred though other salts, such as amine and alkanol amine, can be used if desired.

The condensation products of the present invention and suitable methods for their preparation are fully described in copending application Ser. No. 419,201, filed Dec. 17, 1964, the disclosure of which is incorporated herein by reference. Briefly, the condensation products are prepared by reacting 1,3-butadiene, alone or in admixture with a 2-alkyl-1, 3-butadiene, cyclopentadiene, or an unhindered tertiary mono-olefin, with a solution or suspension of urea in concentrated sulfuric acid and neutralizing the resulting sulfated product.

In addition to the above-described water-soluble condensation products, the detergent compositions of the present invention contain at least one inorganic detergent builder. The term inorganic detergent builder is well known in the art and refers to various inorganic compounds which promote detergent action. Builders which are in use today and which can be used in the detergent compositions of the present invention include alkali metal carbonates such as sodium carbonates, alkali metal bicarbonates, condensed phosphates such as potassium pyrophosphate and sodium polyphosphate, silicates such as sodium silicate and the like. Additives such as water softeners, wetting agents, ion sequestering agents, optical brighteners or chemical bleaching agents, antiredeposition agents such as carboxymethyl cellulose and sodium carboxymethyl cellulose, foaming agents, and the like can also be used. The specific builders and additives and the amounts thereof employed in the detergent composition of the present invention can vary widely and depend to a great extent on economic considerations and on the particular conditions under which the detergent compositions are to be utilized. Excellent results may be obtained with detergent compositions containing a major amount of builder and a minor amount of butadiene condensate.

The detergent compositions of thepresent invention can be'used as solid detergent or in liquid formulations.

The following examples illustrate the manner in which the invention may be practiced, but it is to be understood that such details are given merely for exemplification purposes and are not to be construed as limiting the scope of the appended claims. Unless otherwise indicated, the proportions are expressed in parts by weight. Numbered examples are in accordance with the invention, those designated by letter are inserted for purposes of comparison.

Example I parts sodium salt of a condensation product of 3 moles of butadiene, 1 mole of urea, and 1.5 moles of sulfuric acid and having an acid number of 14, an iodine number of 132, a meltingpoint of 105114 C., 4.96% nitrogen, and 5.24% sulfur are blended with parts sodium tripolyphosphate, 10 parts sodium metasilicate, 39 parts sodium carbonate, and 1 part sodium carboxymethyl cellulose to a fine powder in a Waring Blendor.

The detergency of this blend was tested in 0 and 100 parts per million water hardness (parts per million as Ca CO with 60% as Ca and 40% as Mg) in at Baker Terg-O-Tometer at 120 F. and rpm. using American Conditioning House #119 soiled cloth. The concentration of the detergent composition was 0.25 weight percent. Swatches after washing were dried at 185 F. for one hour followed by conditioning for 24 hours in a constant temperature and humidity room F., 40% R. H.) before reflectance measurements were run.

The wash cycle consisted of placing four swatches (4 x 4 inch) in the preheated detergent (one liter volume), washing for 15 minutes followed by two separate 3 minute rinses. Calculations were:

Percent Increase in Reflectance:

Washed Swatch R-Original R Original R where R=reflectance of swatch Example A Example I was repeated using a branched chain sodium dodecylbenzene-sulfonate (abbreviated hereinafter as SDBS), one of the best detergents in commercial use, in place of the urea-butadiene-sulfuric acid condensate.

Example II Example I was repeated except that a mixture'of 3 moles butadiene and 1 mole isobutylene was substituted for 3 moles of butadiene therein recited. The condensation product after neutralization with sodium hydroxide had an acid number of 1.7, an iodine number of 155, a melting point of 5862 C., 3.65% nitrogen, and 4.3% sulfur.

Example III Example I was repeated except that the urea-butadienesulfuric acid condensate as omitted.

4 The percent increase in reflectance obtained in Examples I, II, III, A, and B are shown in Table I.

TABLE I Percent Increase in Reflectance Example No.

0 ppm. 100 p.p.m. Water Hardness Water Hardness Example IV vTerg-O-Tometer using American Conditioning House cotton soiled cloth. The concentration of the detergent composition was 0.25 weight percent. The increase in reflectance was 130.2%.

Example C Example 'IV was repeated using SDBS in place of the urea-butadiene-sulfuric acid condensate. The increase in reflectance was 130.8%.

Example V Example IV was repeated except that the carboxymethyl cellulose was replaced by sodium carbonate and the concentration of the detergent composition was 1.0% by weight. The increase in reflectance was 117.3%.

Example VI Example V was repeated using the ammonium salt of the urea-butadiene-sulfuric acid condensate instead of the sodium salt. The increase in reflectance was 115.6%.

Example D Example V was repeated using SDBS instead of the urea-butadiene-sulfuric acid condensate. The increase in reflectance was 111.9%.

Thus, it is readily apparent from Example I-VI and A-D, that the detergency of the present urea-olefin-sulfuric acid acid condensation products is equivalent or sufuric acid condensation products is equivalent or supreior to SDBS, one of the most widely used detergents presently in commercial use. In adidtion to having excellent detersive characteristics, these condensation pro-ducts are also less toxic, less irritating and are more readily precipitated by common chemical coagulants, used in sewage treatment than is SDBS.

The results of toxoicological studies on the detergents are shown in Table II, below. The acute oral toxicity was run on mice according to the method of Weil, Litchfield, and Wilcoxon, Biometrics, vol. 8, pp. 249262 (1952), and the Journal of Pharmacology and Experimental Therapeutics, vol. 95, pp. 99-113, (1949). Category of the compounds was judged according to the terminology of Hodge and Sterner, Industrial Hygiene Quarterly, vol. 10, pp. 93-96, (1949) Primary irritation to rabbit skin and eye was determined according to the procedure outlined in Appraisal of the Safety of Chemicals in Foods, Drugs and Cosmetics, Association of Food and Drug Oflicials, US. (1959), pp. 46 and 49. A 60% aqueous solution of the detergents were employed. The interpretation of scoring of irritation to the eye was made according to Kay and Calandra, Journal of the Society of Cosmetic Chemists, pp. 285-286 (1962).

TABLE IL-TOXICOLOGICAL PROPERTIES OF THE DETERGENTS The condensation products of the present invention are readily precipitated by flocculants such as ferric chloride and/ or by contact with soil as illustrated in Table III, below. ,An aqueous solution of 5 p.p.m. detergent was mixed with the indicated amount of FeCl -6H O and/or Delaware soil The slurries were filtered after 24- hours and the amount of detergent in the filtrate determined by the standard Methylene Blue Method (Standard Methods for the Examination of Water and Waste Water, 11th edition, American Public Health Association, Inc., pp. 246- 248).

The detergents of the present invention have a biological oxygen demand value which indicates that they are being degraded whereas SDBS has a zero BOD which indicates no degradation.

The biological oxygen demands of the urea-olefin-sulfruic acid condensation products of the present invention are shown in Table IV.

ing, etc.) should be taken into consideration in order to derive the maximum lbeneficial results The particular builders and the amounts thereof can vary widely and form no part of the present invention that condensation products of urea, sulfuric acid, and butadiene, alone or in admixture with minor amounts of an inhindered tertiary mono-olefin, cyclopentadiene, or 2-alkyl butadiene, can be blended with various builders, to yield a novel and highly-desirable detergent composition.

Although the present invention has been described with reference to particular embodiments and examples, it will be apparent to those skilled in the art that variations and modifications of this invention can be made and that equivalents can be substituted therefor without departing from the principles and true spirit of the invention:

Having described the invention, what is desired to be secured by Letters Patent is:

1. A detergent composition consisting essentially of a major amount of inorganic detergent builder and a minor amount of water-soluble salt of an urea-olefin-sulfuric acid condensation product, said condensation product being prepared by (1) forming a suspension of urea and from 0.75 to 3.0 molar proportions of a sulfuric acid solution containing from 85 to 105 percent by weight of equivalent H 80 in an inert organic diluent; (2) introducing into the said suspension, at with continuous agitation and a temperature of from 10 C. to 70 C., from 0.8 to 10 molar proportions of an olefin selected from the group consisting of 1,3-butadiene and a mixture of a major proportion of 1,3-butadiene and a minor proportion of a member selected from the group consisting of cyclopentadiene, unhindered tertiary mono-olefins, and 2-alkyl 1,3-butadienes wherein the alkyl radical is unbranched 0nd contains from 1 to 3 carbon atoms; (3) and recovering the condensation product from the reaction TABLE IV.-BIOLOGICAL OXYGEN DEMAND OF DETERGENTS Mg. Biological Oxygen Demand as mg. Days Deter- 02 per mg. detergent Seed incngent bation Used SDBS 1 B-U t B-I-U B-I-U 4 24 hour 01d Sewage 3 3 :8; 2 week old sewage g :8; :32 :8:

1 Sodium dodecylbenzene sulionate. 2 Sodium salt of butadiene-urea-suliuric acid condensate.

3 Sodium salt of butadiene-isobutylene-urea-sulfurie acid condensate containing three moles butadiene per mole of isobutylene.

4 Sodium salt of butadiene-isobutylene-urea-suliuric acid condensate containing nine moles butadiene per mole of isobutylene.

Thus, it has been established that the detergent compositions of the present invention have excellent detersive characteristics, are non-toxic and non-irritating, and easily precipitated from aqueous solutions.

The most appropriate builder or mixture of builders,

their proportion to each other, and their concentration in each detergent composition may be suitably determined by routine controls since the beneficial results vary to some degree with changes in formulations. In each case, the proper washing conditions and the intended use of the detergent compositions (e.g. hard or soft water, general home or commercial use, shampoos, machine wash- 5. The detergent composition of claim 2 wherein the inorganic detergent builder is selected from the group consisting of alkali metal carbonates, alkali metal bicarbonates, alkali metal condensed phosphates, alkali metal silicates, and mixtures thereof.

6. A detergent composition consisting essentially of an alkali metal polyphosphate, an alkali metal carbonate, an alkali metal silicate, an alkali metal carboxymethylcellulose, and a compound selected from the group con sisting of alkali metal salts and ammonium salts of an urea-olefin-sulfuric acid condensation product prepared by (l) forming a suspension of urea and from 0.75 to 3.0 molar proportions of a sulfuric acid solution containing from 85 to 105 percent by weight of equivalent H 50 in an inert organic diluent; (2) introducing into the said suspension, with continuous agitation and at a temperature of from l0 C. to 70 C., from 0.8 to 10 molar proportions of an olefin selected from ahe group consisting of 1,3-butadiene and a mixture of a major proportion of 1,3-butadiene and a minor proportion of a member selected from the group consisting of cyclopentadiene, unhindered tertiary mono-olefins, and 2 alkyl 1,3-butadienes wherein the alkyl radical is unbranched and contains from 1 to 3 carbon atoms; (3) and recovering the condensation product from the reaction mixture, all of said molar proportions being per molar proportion of urea.

7. The detergent composition of claim 6 consisting essentially of about 35 parts sodium polyphosphate, about 39 parts sodium carbonate, about 10 parts sodium silicate,

. about 1 part sodium carboxymethylcellulose, and about 15 parts sodium salt of the condensation product, said condensation product being prepared with about four mols of 1,3-butadiene, about 1 mol of urea, and about 1.5 mols of sulfuric acid.

References Cited FQREIGN PATENTS 7/1965 Netherlands.

OTHER REFERENCES Surface Active Agents and Detergents, vol. -II, Schwartz et al,, Interscience PubL, New York, 1958, pp. 288-293, 295-297, 302-307.

LEON D. ROSDOL, Primary Emminer.

S. D. SCHNEIDER, S. E. DARDEN,

Assistant Examiners. 

